Process for preparing resins and products thereof



-ucts containing combined halogen,

Patented Nov. 25, 1941 uurnazn STATES "PATENT' OFFICE PROCESS FORPREPARING RESINS AND monuo'rs 'rnnnnor William J. Sparks, Cranford, andDonald 0. Field, Roselle Park, N. 1., assignorl to Standard OilDevelopment Company, a corporation of Delaware No Drawing. ApplicationNovember 19,

Serial No. 241,332

8 Claims.

This invention relates to novel synthetic resinous polymerization andcondensation prodand to methods for preparing them. Itrelates moreparticularly to the preparation of high molecular weight viscous toplastic, soluble products containing high concentrations of combinedhalogen and to the preparation of such products by subjecting suitableolefin halides or a mixture of such olefin halides and hydrocarbonaliphatic olefins to the action of active polymerization andcondensation catalysts at low temperatures.

The improved polymerization and condensation products of this inventioncontain substantial proportions of combined halogen, correspondingapproximately to the amount in the olefin halides reacting. Theresulting products have the advantage over separately chlorinatedresinous materials in that the chlorine is evenly distributed throughoutthemolecule and is firmly and uniformly held.

The olefin halides used in this invention have the following structure:

CHr-X in which X represents a halogen and R a hydrogen atom or an alkylor aryl group. Examples fate, amino or hydroxy groups.

It has been found that these olefin halides may be polymerized by theaction of metal halide catalysts of the type used in the Friedel-Craftsynthesis. The reaction is conducted at low, temperatures below zero C.to 10 C. and preferably at much lower temperatures such as -40 or -50 to80 C.

The catalyst is preferably dissolved in a suitable organic liquid whichis substantially inert under the conditions of the reaction, forexample, aluminum chloride dissolved in ethyl chloride has been foundparticularly effective in the processes of this invention.

It has also been found that valuable chlorinecontaining co-polymers ofhigh molecular weight,

which are also viscous to plastic,'soluble products. can be formed byconducting the above-described reaction in the presence of low molecularweight oleflns, preferably iso-olefins such as isobutylene.

Instead of isobutylene, other iso-oleflns capable of polymerizing in amanner similar to theiso-' butylene may be used, such as2-methylbutene-1,

Example. 1

Ten volumes of methallyl chloride were diluted with twenty volumes ofethyl chloride (CzHaCl) and the mixture was cooled with powdered carbondioxide snow to -78 C. Four volumes of a concentrated solution ofaluminum chloride in ethyl chloride, prepared at the boiling point ofethyl chloride, was cooled to -'l8'' C. and then added rapidly to thefirst mixturewith stirring. A precipitate formed immediately whichredissolved on standing for two hours. The reaction mixture was thendiluted with alcohol to remove the catalyst and was permitted to warm upto room temperature thereby removing the ethyl chloride by evaporation.The residue was then dissolved in benzol and precipitated by theaddition of ethyl alcohol. This procedure was repeated several times,yielding a product which was a pliable, rather hard resin which softensconsiderably upon heating to about 200 F. The resin is of dark browncolor and is soluble in liquid hydrocarbons, such as benzene, gasoline,and in other solvents, such as carbon tetrachloride and-chloroform. 'Itis insoluble in ethyl alcohol, water and acetone.

Example II the reaction mixture was diluted with alcohol to remove thecatalyst and was permitted to warm up to room temperature, therebyremoving the ethyl chloride" by evaporation. The residue was thendissolved in benzoland precipitated bythe addition of ethyl alcohol.This procedure was repeated several times, the product finallyprecipitating from acetone being dried by heating in an oven at 100 C.This product was a waterwhlte pliable, plastic solid having rubber-likeproperties. It gave a positive Beilstein test for chlorine. It issoluble in solvents such as benzene, gasoline, and carbon tetrachloride.It is insoluble in ethyl alcohol, water, and acetone.

The products prepared according to. this invention have extremely highmolecular weights, generally above about 1000 and usually of much highermolecular weight of the order of 5000 to 50,000. .It is believed thatthese products are characterized by the long carbon chain structurecharacteristic of the extremely high molecular weight polymers ofisobutylene. For example, the products obtained by polymerization ofmethallyl chloride apparently have the following structure:

while the co-polymers prepared from methallyl chloride and isobutyleneapparently have the following structure:

CHI CHaGl CH: C HzCl CHr- CHr-b-CHr- H: H: H: H;

Both the methallyl chloride polymers and the co-polymers arecharacterized by the presence of chlorine in the primary positions only.

As the catalyst, instead of using aluminum chloride, other volatilizableFriedel-Crafts metal halides having a similar catalytic influence onpolymerization and condensation reactions may be used, as, for instance,aluminum bromide, aluminum iodide, titanium tetrachloride, and the like,or complexes of these catalysts with organic compounds, such as ethylchloride. Other compounds which may be used as solvent or as a medium toform complexes with the catalysts include methyl chloride, isopropylchloride, chloroform, sulfuryl chloride (SO2C12), carbon disulphide, andmany polar organic compounds.

In preparing the preferred type of catalyst, such as the AlCla-CzHsCl,it is best to dissolve the aluminum chloride in thyl chloride at roomtemperature because it is relatively insoluble at the operatingtemperatures, e. g., below 50 C. as shown by the solubility data in thetable here below:

Solubility of aluminum chloride in ethyl chloride Contact AlCla SampleTemp time dissolved Ethyl chloride and excess aluminum C. Minutes Percent chloride. 78 60 0. 1 Do 45' 45 0. 1 Do 180 4.4 Do +8 60 5. 4 D0 +12180 7. 4

After a substantial amount of aluminum chloride has been dissolved indesired amount up to the saturation point, the solution, if not alreadyof the proper concentration, may be adjusted by dilution with furthersolvent and then cooled down to the desired temperature for thecatalytic co-polymerization. If desired, the AlCla-CzI-luCl,

either separated as such or else dissolved in ethyl chloride, may bedissolved in or diluted with other solvents or diluents, such as methylchloride, chloroform. etc.

In carrying out both the polymerization and the copolymerizationreactions described above, one suitable procedure is to mix thematerials to be polymerized in the desired proportions, either alone orwith a suitable solvent, diluent, or reirigerant, such as liquefiedethylene, and then add the catalyst, such as a 5% solution of aluminumchloride in ethyl chloride, either alone or dissolved in a suitablediluent such as liquefied ethylene. The use of liquefied ethylene forthe several purposes mentioned has an additional advantage that itserves simultaneously as refrigerant to maintain the desired lowtemperature by absorption of the heat of polymerization by boiling offsome of the liquefied ethylene. If desired, the cooling may be effectedby either internal or external cooling coils through which a suitablerefrigerating liquid is passed or by having the reacting liquids fedinto a pipe, coil, or other condenser immersed in a suitablerefrigerated bath. However, instead of using such a vaporizable diluentor solvent, dry ice (solidified carbon dioxide) may be used asrefrigerant merely by adding pieces of it to the reaction vessel. Owingto the desirability of maintaining a low temperature, it is preferred tohave the catalyst, as well as the reactants, pre-cooled to a temperatureat least as low as the desired operating temperature. If dry ice is usedas refrigerant, the operating temperature is about 78" C., whereas ifliquefied ethylene is used as refrigerant, an operating temperature ofabout C. is maintained (ethylene alone boils at 103 C.) It is possibleto use even lower temperatures by using liquefied methane or mixturesthereof with other hydrocarbons.

If desired, the reaction may be carried out under pressure, either justsufliciently above atmospheric to keep the reactant and solvent in theliquid phase or considerably higher pressures may be used, such as up to10, 20, or 50 atmospheres or more.

In the preparation of co-polymers, the proportions of the materials tobe co-polymerized may vary over wide limits without departing from thescope of the invention. The content of combined chlorine in theco-polymer can thus be controlled by regulating the amounts of methallylchloride and of isobutylene used in the mixture subjected toco-polymerization, the amount of chlorine in the finished productbearing a direct ratio to the proportion of methallyl chloride toisobutylene in the reacted mixture.

The products of this invention are soluble in hydrocarbon oils,generally, and the blends thereof with hydrocarbon oils have manyadvantages. The polymers are extremely efiective, for example, inraising the viscosity and viscosity index of hydrocarbon oils when addedthereto in small proportions of the order of a few per cent. They may beused within the limits of their solubility as thickening agents forgasoline and other motor fuels, burning oils, and lubricants. They alsoserve as plasticizingagents for solid hydrocarbon compositions, such aswaxes, asphalts, and the like. In lubricating oils they have theespecial advantage of decreasing the change in viscosity 'of the oilwith rise in temperature. This is illustrated in the following example:

Example III Two per cent by weight of the co-polymer of methallylchloride and isobutylene, prepared as described in Example II, was addedto an S. A. E. 20-W petroleum lubricating oil. The viscositycharacteristics of the original oil and the resulting blend are given inthe following table:

Saybolt viscosity,

swmds Viscosity index S. A. E. 20-W 276 45.9 13 S. A. E. 20W+2%co-pclymer.-. 518 62.6 91

The products of this invention may also be added in small amounts, ofabout 0.05 to by weight, to lubricating greases and are very effectivein imparting stringy and adhesive characteristics to such greases,including lime, soda, aluminum, and mixed bases.

An illustration of the use of these products in greases is given in thefollowing example:

Example IV ness to metal surfaces and cannot be wiped ofi of suchsurfaces without using much greater pressure than is required for wipingthe same uncompounded greases cleanly from the metal surfaces. Thegreases maintain their improved adhesiveness even at low temperatures ofthe order of --10 F. and lower.

The addition of the products of this invention to lubricating oils andgreases, as described above, also increases the ability of suchlubricant to carry heavy loads and renders them effective lubricantsunder the conditions of extreme pressure encountered in the lubricationof hypoid gears and the like. Sulfur and organic sulfur compounds mayalso be added to such lubricants or th polymerization andco-polymerization product described herein may themselves be sulfurized,as by heating with sulfur or sulfur chloride.

The halogen content of the polymerization and (Io-polymerizationproducts of this invention can be increased by halogenation of suchproducts. For example, these products may be chlorinated by a directreaction with chlorine either in gaseous or dissolved state. Thechlorination is preferably carried out with the products dissolved in aninert solvent, such as carbon tetrachloride. Chlorine may be bubbledthrough this solution under atmospheric pressure'or at higher or lowerpressures, or the solution may be passed in a thin film or spray througha chamber filled with chlorine gas, The chlorination may be conducted inthe absence of light or other catalyzing influence, or it may beconducted in the presence of sunlight or even stronger sources ofultra-violet light, such as a mercury vapor lamp, or in the presence oflight of a carbon arc lamp, or of other light of any desired wavelength, or in the presence of other. catalysts, such as iodine, antimonyhalides, and ferric chloride, or of peroxides, such as benzoyl peroxide,which directs the halogen atoms preferentially to the alpha (end) carbonatoms in the molecule. Mixtures of such catalytic influences may also beused.

Suitable temperatures for the chlorination include from about --50 to C.and range preferably from between about 25 C. and the boiling point ofcarbon tetrachloride, about 78 C. For temperatures below the meltingpoint of carbon tetrachloride, a mixture such as one part of carbontetrachloride and three parts of chloroform may be used. By these meansproducts having chlorine contents as high as 50 to 75% are prepared,depending upon the intensity-of the chlorination conditions and the timeof exposure of the materials to be chlorinated.

If desired the products may be freed from any corrosive constituents,such as free chlorine or decomposition products that may be present, byincorporating therewith a basic material which may also serve as astabilizer, such, for example, as an aromatic amine, monoethyl aniline,methyl naphthylamine, or a quarternary ammonium base, such astetramethyl ammonium hydroxide. The products may also be washed with analkaline solution, such as a 10% solution of sodium hydroxide or sodiumcarbonate.

The polymerization and co-polymerization products of this'invention,whether subjected to additional halogenation or not, are stable towardsunlight and artificial ultra-violet light, air, hot and cold water, andchemical agents, such as solutions of acids, bases, and salts.

The polymerization and co-polymerization products of this invention havethe characteristics, depending on their molecular weight, of viscousliquids to plasticelastic solids. Increasing the halogen content ofthese products, as by chlorination, increases their toughness,chlorinated products of high molecular weight and having chlorinecontents as high as 60 to 75% being obtained in the form of brittlesolids or powders.

The co-polymers of methallyl chloride and isobutylene are soluble in thefollowing solvents:

Diphenyl oxide Vistone (isopropyl ester of fatty acids pro Theseco-polymers are partially soluble in higher ketones (of higher molecularweight than acetone), diethyl ether, and higher molecular weight esters,such as the organic esters or cellulose, and are not soluble in:

The polymers of methallyl chloride have in general the same solubilitycharacteristics as the co-polymei's, but are less soluble in simpleoxyorganlc solvents of low molecular weight, such as acetone, ethylether, ethyl acetate, etc.

The polymers and co-polymers of this invention may be compounded withthe following resinous, asphaltic, and waxy materials:

Drying oil-modified alkyd resin Hydrocarbon resins from petroleum oilsRun Congo copal East India gum #1 Singapore damar Batu East IndiaCyclopentadlene resin Modified phenolic resin Alkyd maleic resin Estergum Rosin Limed rosin Polystyrol Pure phenolics Poly indene Utahgilsonite Coal tar Araclors (chlorinated diphenyl resins) TallowStearine pitch Beeswax Halowax Chlorinated parafiln wax Carnauba waxSpermaceti wax Stearic wax Chinese insect wax Japan wax Ozokerite waxCandleilla wax Montan wax Cumar Polyvinyl acetate Benzyl celluloseMethyl methacrylate Parex resin Asphalt Ceresln wax Lauryl alcoholStearyl alcohol Cetyl alcohol Oleic alcohol Chlorinated rubber They arepartially compatible with ethyl cellulose and are incompatible with:

Cellulose acetate Gum elemi Shellac Manila gum Polyvinyl chloride Thepolymers and co-polymers of this inventlon may be compounded with thefollowing materials commonly used as plasticizers:

Dimethyl phthalate Diethyl phthalate Dibutyl phthalate Trlbutylphosphate Triphenyl phosphate Tricresyl phosphate Dibutyl tartrate Butylstearate Amyl stearate Amyl oleate Raw castor oil Raw linseed oil Rawtung oil Raw soy bean oil Raw cottonseed oil Raw sardine oil Raw perillaoil Raw rape seed oil Methyl phthalyl ethyl glycollate Butyl phthalylethyl glycollate Methyl cyclohexyl adipate Benzyl benzoate TriacetinButyl acetyi ricinoleate Camphor Blown linseed oil Boiled linseed oilBoiled tung oil Blown soy bean 011 They are incompatible with linseedoil fatty acids and with tung oll fatty acids.

As indicated above, the polymerization and co-polymerization products ofthis invention are high molecular weight hydrocarbons containingsubstantial proportions of combined halogen and ar either viscousliquids or solids or substances of, more or less, intermediatecharacteristics in the nature of plastic solids, depending on the natureof the original material treated, the duration and type of treatment,and the extent of any further halogenation. These products may be usedfor a wide variety of purposes. For example, they may be used asfire-resistant agents, for impregnating various types of porous orfibrous materials, such as cloth, paper, and building materials. Theymay also be mixed with inert organic materials and added to solutions ofartificial silk for the purpose of delustering the silk product. Theymay also be incorporated with wax and used for impregnating wood forpreservation purposes.

They are soluble in many volatile solvents V which are used in thepreparation of coating compositions of various kinds, and may be usedtherewith, alone, or in conjunction with other resins, impregnating orcoating materials, table coatings, insulating compounds, lubricating oilthickeners, etc., or they may be added in proportions of 5, 10,. 50 oreven 95% to rubbers such as natural rubber, polychlorprene, polyolefinesulfide type rubber, ethylene dichloride-benzol type rubber,'polysuli'ones, polystyrol, polyvinyl compounds, polyacrylates,polydiolefines, chlorinated or fiuorinated polymers, resins, cellulosecompounds, rubber hydrochlorides or haloformed rubbers oi the Pliolitetype. They may be vulcanized with the above compounds to give rubberyorebonite-like products.

The halogen atoms attached to the polymer or co-polymer may also besubiectd to metathetical reactions to g ve modified products havinhydroxyl, nitrile, mercaptyl, or ester groups in place of the chlorineatoms.

This invention is .not to be limited to any specific examples ortheoretical explanation presented above, all such being intended solelyfor purpose of illustration, but is to be limited only to. the followingclaims in which it is desired to claim all novelty insofar as the priorart permits.

We claim: 1. Process for preparing improved viscous liquid to solidresinous products, comprising polymerizing an olefin halide representedby the formula,

Clix-X 3. Process according; to claim 1 in which the said polymerizationreaction is conducted at a temperature below about-40 C.

4. Process for preparing improved viscous liq-- uid to solid resinousproducts, comprising polymerizing an olefin chloride represented by theformula, I

cmol

=cm R in which R represents an alkyl group, at a temperature below about40 C. in the presence of a solution of aluminum chloride in ahydrocarbon W chloride solvent.

5. Process according to claim 4 in which said hydrocarbon chloridesolvent is ethyl chloride.

6. Resinous products containing combined halogen and having theproperties of viscous 1iq.

uids to solids of high molecular weight, produced by polymerization ofan olefin halide represented by the formula,

Clix-X

